This invention relates to fluorochemical copolymers and their application to fabrics and fabric blends to impart soil release properties.
Fabric soiling, always a problem with textiles, became even more of a problem with the advent of permanent press fabrics composed of cotton-synthetic blends. These are treated with various additives, which often make them more difficult to clean. In addition, permanent press fabrics are best laundered at low temperatures and mild agitation, whereas soil is best removed at higher temperatures and vigorous agitation. For these reasons, various soil release agents are frequently applied to such fabrics to aid in removing soil during laundering. Preferably, these soil release agents are not themselves removed during laundering (i.e., are durable), and either improve or do not harm other desired properties of the fabric.
Fluorochemicals, despite their comparatively high cost, are probably the most widely used soil release agents on cellulosic fabrics because of their performance at low concentration, their compatibility with permanent press finishes, and freedom from most undesired side effects. However, these agents also tend to affect the hydrophilicity and oleophobicity (i.e., the water and oil repellency) of the fabrics in ways that may be desirable for some applications but undesirable for others. For example, hydrophilic soil releasers are useful to maintain the desired wicking of moisture from skin that fabrics provide, but such hydrophilicity may not be desirable for some other applications such as outerwear. Balancing these characteristics to achieve the desired properties for certain applications while maintaining good soil release properties is often difficult.
A widely used class of soil release fluorochemicals is composed of perfluorinated urethanes containing polyethylene oxide moieties. Such urethanes and their intermediate isocyanates are costly and potentially hazardous to manufacture. The urethane type products are often repellent as well as soil releasing, and thus reduce the comfort of wearing cotton or similar garments. These existing products are difficult to modify when it is desired to increase the degree of hydrophilicity of the fabric for a particular application.
Fluorochemicals which are not urethane based have been used for oil and water repellency in the paper industry. U.S. Pat. No. 5,674,961 of Fitzgerald discloses a class of fluorochemical copolymers useful for improving the water, oil and grease resistance of paper. None of the information in this patent suggests that such a copolymer might be useful as a soil release agent, an entirely different type of application than grease-proofing paper. U.S. Pat. No. 4,147,851 of Raynolds teaches fluorochemical copolymers useful for oil and water repellency applications for paper and fabrics. Again, there is no suggestion that these copolymers are useful as a soil release agent.
Soil release fluorochemicals which are as effective as the perfluorinated urethanes, but which do not involve costly and potentially hazardous isocyanate/urethane chemical manufacturing processes are highly desirable and would have widespread applications. Even more desirably, such a soil release agent would be made by a process, which makes it easier to modify the degree of hydrophilicity of the agent and treated fabric over a wide range to suit various applications. The present invention provides such soil release fluorochemicals.
The present invention comprises a copolymer composition, which imparts soil release properties to fabrics and fabric blends comprising monomers copolymerized in the following percentages by weight:
(a) from about 30% to about 49% of at least one monomer of formula I:
Rfxe2x80x94Qxe2x80x94Axe2x80x94C(O)xe2x80x94C(R)xe2x95x90CH2xe2x80x83xe2x80x83I 
wherein
Rf is a straight or branched-chain perfluoroalkyl group of from 2 to about 20 carbon atoms,
R is H or CH3,
A is O, S or N(Rxe2x80x2), wherein Rxe2x80x2 is H or an alkyl of from 1 to about 4 carbon atoms,
Q is alkylene of 1 to about 15 carbon atoms, hydroxyalkylene of 3 to about 15 carbon atoms, xe2x80x94(CnH2n)(OCqH2q)mxe2x80x94, xe2x80x94SO2xe2x80x94NRxe2x80x2(CnH2n)xe2x80x94, or
xe2x80x94CONRxe2x80x2(CnH2n)xe2x80x94, wherein Rxe2x80x2 is H or an alkyl of from 1 to about 4 carbon atoms, n is 1 to about 15, q is 2 to about 4, and m is 1 to about 15;
(b) from about 10% to about 70% of at least one monomer or a mixture of monomers selected from formula IIA, formula IIB, and formula IIC:
(R1)2Nxe2x80x94(CH2)rxe2x80x94Zxe2x80x94C(O)xe2x80x94C(R2)xe2x95x90CH2xe2x80x83xe2x80x83IIA 
(O)(R3)(R4)Nxe2x80x94(CH2)rxe2x80x94Zxe2x80x94C(O)xe2x80x94C(R2)xe2x95x90CH2xe2x80x83xe2x80x83IIB 
Xxe2x88x92(R5)(R4)(R3)N+xe2x80x94(CH2)rxe2x80x94Zxe2x80x94C(O)xe2x80x94C(R2)xe2x95x90CH2xe2x80x83xe2x80x83IIC 
wherein
Z is xe2x80x94Oxe2x80x94 or xe2x80x94NR5xe2x80x94; R1 is an alkyl group of from 1 to about 3 carbon atoms; R2 is H or an alkyl radical of 1 to about 4 carbon atoms; R3 and R4 are each an alkyl of 1 to 4 carbon atoms, hydroxyethyl, benzyl, or R3 and R4 together with the nitrogen atom form a morpholine, pyrrolidine, or piperadine ring; R5 is H or an alkyl of 1 to 4 carbon atoms, or R3, R4 and R5 together with the nitrogen atom form a pyridine ring; r is 2 to 4; and wherein for formula IIA the nitrogen is from about 40% to 100% salinized; and,
(c) from 0% to about 7% of a monomer of the formula III, IV, V, or VI or a mixture thereof: 
Clxe2x80x94CH2xe2x80x94CH(OH)CH2xe2x80x94Oxe2x80x94C(O)xe2x80x94C(R2)xe2x95x90CH2xe2x80x83xe2x80x83IV; 
(R6)OC(O)C(R6)xe2x95x90CH2xe2x80x83xe2x80x83V; 
or 
CH2xe2x95x90CCl2xe2x80x83xe2x80x83VI 
wherein
each R2 is independently H or an alkyl radical of 1 to about 4 carbon atoms and each R6 is independently H or an alkyl of 1 to about 8 carbon atoms.
The present invention further comprises a method of treating fabrics and fabric blends to impart soil release properties comprising application to the surface of the fabric or blended fabric of an effective amount of the copolymer composition comprising monomers copolymerized in the following percentages by weight:
(a) from about 30% to about 90% of at least one monomer of formula I:
Rfxe2x80x94Qxe2x80x94Axe2x80x94C(O)xe2x80x94C(R)xe2x95x90CH2xe2x80x83xe2x80x83I 
wherein
Rf is a straight or branched-chain perfluoroalkyl group of from 2 to about 20 carbon atoms,
R is H or CH3,
A is O, S or N(Rxe2x80x2), wherein Rxe2x80x2 is H or an alkyl of from 1 to about 4 carbon atoms,
Q is alkylene of 1 to about 15 carbon atoms, hydroxyalkylene of 3 to about 15 carbon atoms, xe2x80x94(CnH2n)(OCqH2q)mxe2x80x94, xe2x80x94SO2xe2x80x94NRxe2x80x2(CnH2n)xe2x80x94, or
xe2x80x94CONRxe2x80x2(CnH2n)xe2x80x94, wherein Rxe2x80x2 is H or an alkyl of from 1 to about 4 carbon atoms, n is 1 to about 15, q is 2 to about 4, and m is 1 to about 15;
(b) from about 10% to about 70% of at least one monomer or a mixture of monomers selected from formula IIA, formula IIB, and formula IIC:
(R1)2Nxe2x80x94(CH2)rxe2x80x94Zxe2x80x94C(O)xe2x80x94C(R2)xe2x95x90CH2xe2x80x83xe2x80x83IIA 
(O)(R3)(R4)Nxe2x80x94(CH2)rxe2x80x94Zxe2x80x94C(O)xe2x80x94C(R2)xe2x95x90CH2xe2x80x83xe2x80x83IIB 
Xxe2x88x92(R5)(R4)(R3)N+xe2x80x94(CH2)rxe2x80x94Zxe2x80x94C(O)xe2x80x94C(R2)xe2x95x90CH2xe2x80x83xe2x80x83IIC 
wherein
Z is xe2x80x94Oxe2x80x94 or xe2x80x94NR5xe2x80x94; R1 is an alkyl group of from 1 to about 3 carbon atoms; R2 is H or an alkyl radical of 1 to about 4 carbon atoms; R3 and R4 are each an alkyl of 1 to 4 carbon atoms, hydroxyethyl, benzyl, or R3 and R4 together with the nitrogen atom form a morpholine, pyrrolidine, or piperadine ring; R5 is H or an alkyl of 1 to 4 carbon atoms, or R3, R4 and R5 together with the nitrogen atom form a pyridine ring; r is 2 to 4; and wherein for formula IIA the nitrogen is from about 40% to 100% salinized; and,
(c) from 0% to about 7% of a monomer of the formula III or IV, or a mixture thereof: 
Clxe2x80x94CH2xe2x80x94CH(OH)CH2xe2x80x94Oxe2x80x94C(O)xe2x80x94C (R2)xe2x95x90CH2xe2x80x83xe2x80x83IV; 
(R6)OC(O)C(R6)xe2x95x90CH2xe2x80x83xe2x80x83V; 
or 
CH2xe2x95x90CCl2xe2x80x83xe2x80x83VI 
wherein
each R2 is independently H or an alkyl radical of 1 to about 4 carbon atoms, and each R6 is independently H or an alkyl of 1 to about 8 carbon atoms.
The present invention further comprises a fabric or fabric blend which has been treated according to the method of the present invention as described above. The treated fabric or fabric blend has a fluorine content of from about 0.05% to about 0.5% by weight.
This invention comprises improved fluorochemical copolymers useful for imparting soil release properties to fabrics or blends. By xe2x80x9cfabricsxe2x80x9d is meant natural or synthetic fabrics composed of fibers of cotton, rayon, silk, wool, polyester, polypropylene, polyolefins, nylon, and aramids such as xe2x80x9cNOMEXxe2x80x9d and xe2x80x9cKEVLAR.xe2x80x9d By xe2x80x9cfabric blendsxe2x80x9d is meant fabric made of two or more types of fibers. Typically these blends are a combination of a natural fiber and a synthetic fiber, but also can include a blend of two natural fibers or of two synthetic fibers. Trademarks and tradenames are indicated herein by capitalization. Superior soil release properties, along with desirable properties of repellency and wicking can be imparted to fabrics and fabric blends by the addition of certain fluorochemical copolymers. These can be applied to the fabric in the form of a self-dispersed emulsion or dispersion in water or other solvent either before, after or during the application of other fabric treatment chemicals.
The highly efficient copolymers useful for this purpose are characterized in that they contain copolymerized comonomers in the following percentages by weight, relative to the total weight of the copolymers:
(a) from about 30% to about 90% of at least one monomer of formula I:
Rfxe2x80x94Qxe2x80x94Axe2x80x94C(O)xe2x80x94C(R)xe2x95x90CH2xe2x80x83xe2x80x83I 
wherein
Rf is a straight or branched-chain perfluoroalkyl group of from 2 to about 20 carbon atoms,
R is H or CH3,
A is O, S or N(Rxe2x80x2), wherein Rxe2x80x2 is H or an alkyl of from 1 to about 4 carbon atoms,
Q is alkylene of 1 to about 15 carbon atoms, hydroxyalkylene of 3 to about 15 carbon atoms, xe2x80x94(CnH2n)(OCqH2q)mxe2x80x94, xe2x80x94SO2xe2x80x94NRxe2x80x2(CnH2n)xe2x80x94, or
xe2x80x94CONRxe2x80x2(CnH2n)xe2x80x94, wherein Rxe2x80x2 is H or an alkyl of from 1 to about 4 carbon atoms, n is 1 to about 15, q is 2 to about 4, and m is 1 to about 15;
(b) from about 10% to about 70% of at least one monomer or a mixture of monomers selected from formula IIA, formula IIB, and formula IIC:
(R1)2Nxe2x80x94(CH2)rxe2x80x94Zxe2x80x94C(O)xe2x80x94C(R2)xe2x95x90CH2xe2x80x83xe2x80x83IIA 
(O)(R3)(R4)Nxe2x80x94(CH2)rxe2x80x94Zxe2x80x94C(O)xe2x80x94C(R2)xe2x95x90CH2xe2x80x83xe2x80x83IIB 
Xxe2x88x92(R5)(R4)(R3)N+xe2x80x94(CH2)rxe2x80x94Zxe2x80x94C(O)xe2x80x94C(R2)xe2x95x90CH2xe2x80x83xe2x80x83IIC 
wherein
Z is xe2x80x94Oxe2x80x94 or xe2x80x94NR5xe2x80x94; R1 is an alkyl group of from 1 to about 3 carbon atoms; R2 is H or an alkyl radical of 1 to about 4 carbon atoms; R3 and R4 are each an alkyl of 1 to 4 carbon atoms, hydroxyethyl, benzyl, or R3 and R4 together with the nitrogen atom form a morpholine, pyrrolidine, or piperadine ring; R5 is H or an alkyl of 1 to 4 carbon atoms, or R3, R4 and R5 together with the nitrogen atom form a pyridine ring; r is 2 to 4; and wherein for formula IIA the nitrogen is from about 40% to 100% salinized; and,
(c) from 0% to about 7% of a monomer of the formula III, IV, V, or VI, or a mixture thereof: 
Clxe2x80x94CH2xe2x80x94CH(OH)CH2xe2x80x94Oxe2x80x94C(O)xe2x80x94C (R2)xe2x95x90CH2xe2x80x83xe2x80x83IV; 
(R6)OC(O)C(R6)xe2x95x90CH2xe2x80x83xe2x80x83V; 
or 
CH2xe2x95x90CCl2xe2x80x83xe2x80x83VI 
wherein
each R2 is independently H or an alkyl radical of 1 to about 4 carbon atoms, and each R6 is independently H or an alkyl of 1 to about 8 carbon atoms.
Preferably the monomer of formula I is a perfluoroalkylethyl acrylate. More preferably the perfluoroalkyl carbon chain length distribution by weight is about 50% of 8-carbon, about 29% of 10-carbon, about 11% of 12-carbon, and with smaller percentages of 6-carbon, 14-carbon and longer chain lengths.
The proportion of monomer (a) of formula I is at least about 30% relative to the total weight of copolymer. If it is present in lower amounts, the polymer becomes more hydrophilic and the oil repellency drops off to an undesirable level. In the method and treated fabric or fabric blend of the present invention the proportion of monomer (a) of formula I is less than about 90%. If it is present in higher amounts, the amounts of the solubilizing monomer (b) of formula IIA and/or IIB will be too low, resulting in poor dispersability. In the copolymer composition of the present invention the proportion of monomer (a) of formula I in the copolymer is between about 30% and about 49% by weight. This latter range is preferred for the best balance of soil release, hydrophilicity and oleophobicity in currently envisioned applications of treatment of fabrics and fabric blends. More preferably the proportion of monomer (a) of formula I in the copolymer is between about 30% and about 45% by weight. Other proportions may be more desirable for other applications.
In fact, one of the major advantages of the inventive composition is that its hydrophilic and oleophobic properties can be varied over a wide range for different applications by simply varying the relative amounts of monomers (a) of formula I and (b) of formula IIA and/or IIB, while still maintaining its properties as an effective soil release agent. That is, the copolymer is modified to make the treated fabric more oleophobic and water repellent by increasing the proportion of monomer (a) of formula I within the above range, or is modified to make the treated fabric more hydrophilic (thereby improving wicking) by increasing the proportion of monomer (b) of formula IIA and/or IIB. This flexibility has not been found possible with existing, more expensive soil release agents.
Preferably monomer (b) of formula IIA is derived from diethylaminoethyl methacrylate by partial or full salinization. The free amine portions of the resulting copolymer is then reacted with a salinizing agent such as acetic acid, resulting in the conversion of part or all of the amine moieties to the corresponding acetate. It must be at least about 40% salinized for adequate solubilizing effect, but may be as high as 100%. Preferably the degree of salinization is between about 50% and about 100%. Alternatively, the salinization reaction is carried out on the amine group before the polymerization reaction with equally good results. The salinizing group is an acetate, halide, sulfate, tartarate or other known salinizing group.
The proportion of monomer (b) of formula IIA, IIB, IIC or a mixture thereof must be at least about 10% for adequate solubilization. While a copolymer with proportions of this monomer (b) above about 70% may be satisfactory in soil releasing properties, such a proportion will produce polymers with very high viscosity, making processing and handling difficult. Preferably the proportion of monomer (b) of formula IIA, IIB, IIC or a mixture thereof in the copolymer is between about 50% and about 65% by weight for the best balance of soil release, hydrophilicity, oleophobicity and viscosity in currently envisioned applications. Other proportions may be more desirable for other applications. All weight percentages are based on the monomer weight as quaternized.
The amine oxide monomers of formula IIB have the formula (O)(R3)(R4)Nxe2x80x94(CH2)rxe2x80x94Zxe2x80x94C(O)xe2x80x94C(R2)xe2x95x90CH2 as described hereinabove wherein NR3R4(O) represents 
They are prepared by reacting the aforesaid acrylate or methacrylate ester or corresponding acrylamide or methacrylamide with conventional oxydizing agents such as hydrogen peroxide or peracetic acid.
The quaternary ammonium monomers of formula IIC are prepared by reacting the acrylate or methacrylate esters or corresponding acrylamide or methacrylamide with a di-(lower alkyl) sulfate, a lower alkyl halide, trimethylphosphate or triethylphosophate. Dimethyl sulfate and diethyl sulfate are preferred quaternizing agents.
The presence of monomer (c) of formula III, IV, V, or VI is optional, depending on the particular application for the copolymer. While there are some applications for which it is not necessary, for most of the presently envisioned applications it is present to achieve satisfactory bonding to the fibers. While not wishing to be bound by this theory, it is believed that monomer (c) of formula III and IV acts as a reactive site for the polymer to covalently bond to the substrate surface. Monomers V and VI can be incorporated to improve the compatability of the copolymer with the fabric substrate. To have a noticeable effect on this property, it must be present in a proportion of at least about 1%. An amount above about 7% is unnecessary and may not further improve this performance. Preferably, for many applications, the proportion of monomer (c) of formula III, IV, V or VI in the copolymer is from about 1% to about 5% by weight. Preferably (c) is glycidyl methacrylate. The monomers of formula III, IV, V and VI are prepared by conventional methods known in the art.
The polymerization of comonomers (a), (b) and (c) is carried out in a solvent such as acetone, methylisobutyl ketone, ethyl acetate, isopropanol, and other ketones, esters and alcohols. The polymerization is conveniently initiated by azo initiators such as 2,2xe2x80x2-azobis(2,4-dimethylvaleronitrile). These initiators are sold by E. I. du Pont de Nemours and Company, Wilmington, Del., commercially under the name of xe2x80x9cVAZOxe2x80x9d 67, 52 and 64, and by Wako Pure Industries, Ltd., Richmond, Va., under the name xe2x80x9cV-501.xe2x80x9d
The present invention further comprises a method of treating fabrics or fabric blends comprising application to the surface of the fabric or fabric blend of an effective amount of a copolymer as described above. The copolymers are applied to the fabric or blended fabric to be treated from aqueous dispersions, either alone or in a mixture with other textile treatment agents or finishes. The dispersions are generally applied to textile fabrics by spraying, dipping, padding, or other well-known methods. After excess liquid has been removed, for example by squeeze rolls, the treated fabric is dried and then cured by heating, for example, to 100xc2x0 C. to 190xc2x0 C., for at least 30 seconds, typically 60-180 seconds. Such curing enhances soil release and durability of the soil release. While these curing conditions are typical, some commercial apparatus may operate outside these ranges because of its specific design features.
The present invention further comprises a fabric or fabric blend which has been treated to impart soil release properties thereto by application of an effective amount of a copolymer as described above. The treated fabric has a fluorine content of from about 0.05% to about 0.5% by weight. The treated fabric has superior soil release properties along with desirable properties of repellency and wicking.
The copolymers and method of the present invention are useful to enhance soil release from fabrics and fabric blends during laundering. The soil release property is durable, and is especially effective for permanent press fabric blends. The treated fabrics and fabric blends of the present invention are useful in a variety of applications such as for textiles, clothing, furnishings and the like. The copolymers of the present invention are advantageous in that they are safer to manufacture than the isocyanate type copolymer, and that it is easy to adjust the degree of hydrophilicity of the copolymer and treated fabric or fabric blend over a wide range by modifying the level of monomers of formulae I versus IIA and IIB allowing for a variety of end use applications. The inventive compositions are made at lower materials cost than isocyanate-based soil release agents, in part because the gas/liquid reactions required for manufacturing phosgene and isocyanates are eliminated.
The following tests were employed in evaluating the examples herein.
Soil Release
The copolymer materials were tested as a soil release agent as described in AATCC 130-1981, designed to measure the ability of a fabric to release oily stains during a typical home laundering. In this method, an oily stain on a test specimen is produced by using a weight to force a given amount of stain into the fabric. The soiled fabric is laundered, and the residual stain is compared to a scale from 1 to 5 using a standard soil release replica. The number 5 represents the most effective soil release properties and the number 1 the least. Intermediate values are assigned between 1 and 5.
Specifically, the tests are carried out as follows. Five drops of a specific oily soiling agent are placed in the approximate center of a test specimen of fabric. Then a square of glassine paper is placed over the fabric, covering the puddle, followed by a 5 lb (2.3 Kg) weight over the glassine paper. This is allowed to sit for 60 seconds, then the weight and glassine paper are removed. The test specimen is then washed within 15 to 60 minutes at a temperature of 41xc2x0 C. using 140 grams of detergent xe2x80x9cTidexe2x80x9d available from Procter and Gamble Company, Cincinnati, Ohio, in a standard washer, along with test specimen ballast to make a total weight of 1.8 Kg, for a period of 12 minutes. The entire washer load of specimen and ballast is then placed in a dryer and dried at a maximum air outlet temperature of 70xc2x0 C. for 45 minutes. The dried test samples are then judged in comparison to the standard scale as described above.
Water Repellency
The water repellency of a treated substrate was measured according to the DuPont technical Laboratory Method as outlined in the Teflon (copyright) Global Specifications and Quality Control Tests information packet. The test determines the resistance of a treated substrate to wetting by aqueous liquids. Drops of water-alcohol mixtures of varying surface tensions are placed on the fabric and the extent of surface wetting is determined visually. The test provides a rough index of aqueous stain resistance. The higher the water repellency rating, the better the resistance of a finished substrate to staining by water-based substances. The composition of standard test liquids is shown in the following table.
Oil Repellency
The treated fabric samples were tested for oil repellency by a modification of AATCC standard Test Method No. 118, conducted as follows. A fabric sample, treated with an aqueous dispersion of polymer as previously described, is conditioned for a minimum of 2 hours at 23xc2x0 C.+20% relative humidity and 65xc2x0 C.+10% relative humidity. A series of organic liquids, identified below in Table I, are then applied dropwise to the fabric samples. Beginning with the lowest numbered test liquid (Repellency Rating No. 1), one drop (approximately 5 mm in diameter or 0.05 mL volume) is placed on each of three locations at least 5 mm apart. The drops are observed for 30 seconds. If, at the end of this period, two of the three drops are still spherical in shape with no wicking around the drops, three drops of the next highest numbered liquid are placed on adjacent sites and similarly observed for 30 seconds. The procedure is continued until one of the test liquids results in two of the three drops failing to remain spherical to hemispherical, or wetting or wicking occurs.
The oil repellency rating of the fabric is the highest numbered test liquid for which two of the three drops remained spherical to hemispherical, with no wicking for 30 seconds. In general, treated fabrics with a rating of 5 or more are considered good to excellent; fabrics having a rating of one or greater can be used in certain applications.
The following preparative examples were used in evaluating the properties of fabric and fabric blends treated with the inventive copolymers and comparative copolymers.